Titanium esters react with high molecular weight hydroxyl-containing compounds so as to cross-link them and produce gels, J. Oil and Colour Chem. Assoc. 31, 405 (1948). As the cross-linking rate of simple alkyl esters of titanium is too fast for some industrial uses, it has been depressed by combining titanium esters with a variety of multifunctional compounds; e.g., the complex condensation products prepared by Shacklett, U.S. Pat. No. 2,870,181, by reacting an organotitanate with an .alpha.-hydroxy carboxylic acid such as lactic acid; the organic titanate chelates obtained by reacting alkyl titanates with 2,4-pentanedione or an acetoacetate, U.S. Pat. No. 2,680,108; also those prepared by reacting alkyl titanates with alkanolamines, U.S. Pat. Nos. 2,950,174 and 3,301,723.
The production of oil and gas can be stimulated by a technique, known as hydraulic fracturing, in which a fluid composition is introduced into an oil- or gas-containing subterranean formation at a flow rate and pressure which create and/or extend a fracture into the formation. The fluid composition usually carries a proppant (e.g., sand, bauxite, etc.) which is forced into the fracture by the fluid composition and prevents closure of the fracture after the fluid pressure is released. For example, Tiner, et al., U.S. Pat. No. 3,888,312, disclose effecting hydraulic fracturing of a subterranean formation by using an aqueous gel prepared from a solvatable polysaccharide which had been cross-linked with an organotitanate chelate prepared by reacting tetraisopropyl titanate with triethanolamine. The rate at which such aqueous gels are cross-linked by such an organotitanate chelate can be retarded further by adding a polyol to the aqueous gel prior to admixing it with such an organotitanate chelate, Hollenbeak et al., U.S. Pat. No. 4,464,270. On the other hand, Conway, U.S. Pat. No. 4,462,917, retarded the cross-linking rate of that same organotitanate chelate by admixing it with a polyol and aging the admixture for 3 to 12 weeks prior to combining the same with the aqueous gel.
The fluid composition used in hydraulic fracturing comprises an aqueous fluid (usually water or aqueous alcohol), a polymeric gelling agent (e.g., a solvatable polysaccharide), and a cross-linking agent. The aqueous fluid is used to solvate the gelling agent, and the solvated gelling agent, which is to be cross-linked, is typically referred to as the "base gel." The pH of the base gel can be adjusted with various buffering agents prior to cross-linking. The rate of cross-linking determines the rate of viscosity development in the fluid composition. It is desirable to control the rate of cross-linking so that the development of viscosity is delayed until the composition is placed in the subterranean formation.
Several factors influence rate of cross-linking. It is directly proportional to the concentration of the polymeric gelling agent and the temperature of the base gel, so that an increase in the gelling agent concentration or the gel temperature causes an increase in the rate of cross-linking. 0n the other hand, as the temperature of the subterranean formation is cooled by injection of the fluid composition, the rate of cross-linking decreases. The pH of the base gel has its effect on cross-linking as well; as the pH of the base gel increases from 7.0 to 8.5, the rate of cross-linking increases. Because more than one batch of base gel is used in any fracturing job, and because conditions such as base gel temperature and formation temperature vary from job to job and with the time of year, it is desirable to use a cross-linking agent or agents which have a variable or adjustable rate of cross-linking to compensate for these changes and provide a reproducible viscosity development time after time.
Cross-linking agents having a high rate of cross-linking may give a cross-linked gel (e.g., from hydroxypropyl guar) which exhibits poor retention of viscosity with time, also with increased temperature. Moreover, use of such high rate cross-linkers may give gels which develop high viscosity while the gel is being pumped down to the subterranean formation, resulting in shear degradation which reduces or destroys the capacity of the base gel to maintain the proppant (e.g., sand) in suspension. As a consequence, the proppant may drop out of suspension (a "screen-out") and may block the bottom of the well tubing. Excessively high viscosities are not encountered in pumping gels cross-linked with low rate cross-linkers, and therefore such cross-linkers avoid shear degradation. But one may none-the-less experience screen-outs with the use of low rate cross-linkers because the gel fails ever to reach a viscosity high enough to keep the proppant in suspension while being pumped down into the formation.